CN114361452B - Adhesive, electrode slurry, and manufacturing method and application thereof - Google Patents
Adhesive, electrode slurry, and manufacturing method and application thereof Download PDFInfo
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- CN114361452B CN114361452B CN202111537233.1A CN202111537233A CN114361452B CN 114361452 B CN114361452 B CN 114361452B CN 202111537233 A CN202111537233 A CN 202111537233A CN 114361452 B CN114361452 B CN 114361452B
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Abstract
The application belongs to the technical field of battery manufacturing, and discloses an adhesive, electrode slurry and a manufacturing method thereof. The adhesive comprises polytrifluoroethylene and polyether ether ketone. The electrode paste includes the binder. Through the synergistic effect of the poly (chlorotrifluoroethylene) and the polyether-ether-ketone, the electrode slurry provided by the application has better fluidity and stability, and the problems of gel, jelly and agglomeration are avoided; the surface of the electrode plate has no agglomeration phenomenon, good toughness, low punching rejection rate, good baking effect, simple preparation method and easy industrialization realization.
Description
Technical Field
The application belongs to the technical field of battery manufacturing, and particularly relates to an adhesive, electrode slurry, a manufacturing method and application thereof.
Background
The lithium ion battery has the advantages of small volume, high voltage, high energy density and the like, and is widely applied to the fields of mobile phones, notebooks, electric vehicles and the like. Among the numerous positive electrode active materials used in the lithium ion battery, the lithium nickel cobalt manganese ternary material and the lithium nickel cobalt aluminum ternary material which are in a layered structure are recognized as one of the best choices of the positive electrode active materials of the future power lithium ion battery due to the characteristics of high discharge capacity, good safety performance, stable structure and the like.
Polyvinylidene fluoride (PVDF) is a homopolymer of vinylidene fluoride, is a tough thermoplastic engineering plastic, has special properties such as high temperature resistance, super weather resistance, corrosion resistance, stain resistance, chemical inertness, extremely low surface energy, piezoelectricity, dielectric property, thermoelectric property and the like, and is widely applied to the manufacturing field of lithium ion batteries.
Compared with the traditional lithium cobaltate and lithium manganate, the lithium nickel cobalt manganese ternary material and the lithium nickel cobalt aluminum ternary material have higher pH values, and fluorine in polyvinylidene fluoride is easy to be attacked by OH-in the stirring process of the polyvinylidene fluoride adhesive, so that gel, jelly and agglomeration occur in the processing process of an electrode slice, and the performance of a lithium ion battery is further influenced.
Accordingly, there is a need to provide a binder that improves the quality of lithium ion batteries.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the prior art described above. Therefore, the application provides the adhesive, the electrode slurry, the manufacturing method and the application thereof, and the electrode slurry has better fluidity and stability, effectively solves the problems of gel, jelly and agglomeration in the processing process of the electrode sheet, improves the qualification rate of production, and further improves the quality of the lithium ion battery.
To achieve the above object, a first aspect of the present application provides an adhesive comprising polytrifluoroethylene and polyetheretherketone.
According to some embodiments of the application, the adhesive comprises, in parts by weight, 1.5-6 parts of polytrifluoroethylene and 1 part of polyetheretherketone.
According to some embodiments of the application, the adhesive comprises, in parts by weight, 2-4 parts of polytrifluoroethylene and 1 part of polyetheretherketone.
According to some embodiments of the application, the adhesive has a viscosity of 1000-80000 Pa.S.
According to some embodiments of the application, the binder is applied to the electrode slurry.
According to some embodiments of the application, the electrode slurry comprises an active material and the binder described above.
According to some embodiments of the application, the weight ratio of active substance to binder is 1: (16-99).
According to some embodiments of the application, the electrode slurry is a positive electrode slurry; the active material is a lithium-containing metal oxide.
According to some embodiments of the application, the active material is at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel manganate, lithium iron manganese phosphate, lithium ferrite, lithium nickel cobalt manganese ternary material, lithium nickel cobalt aluminum ternary material, and lithium-rich manganese-based material.
According to some embodiments of the application, the active material is at least one of a lithium nickel cobalt manganese ternary material, a lithium nickel cobalt aluminum ternary material, and a lithium-rich manganese-based material.
A second aspect of the present application provides an electrode slurry comprising an active material and the binder described above.
According to some embodiments of the application, the electrode slurry includes 1 part of active material and 16-99 parts of binder in parts by weight.
According to some embodiments of the application, the electrode slurry is a positive electrode slurry; the active material is a lithium-containing metal oxide.
According to some embodiments of the application, the active material is at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel manganate, lithium iron manganese phosphate, lithium ferrite, lithium nickel cobalt manganese ternary material, lithium nickel cobalt aluminum ternary material, and lithium-rich manganese-based material.
According to some embodiments of the application, the active material is at least one of a lithium nickel cobalt manganese ternary material, a lithium nickel cobalt aluminum ternary material, and a lithium-rich manganese-based material.
According to some embodiments of the application, the electrode slurry further comprises a solvent. Preferably, the solvent is N-methylpyrrolidone and/or xylene.
According to some embodiments of the application, the solvent comprises 1 part N-methylpyrrolidone and 1 part xylene by weight.
According to some embodiments of the application, the weight ratio of solvent to binder is (8-10): 1; preferably, the weight ratio of solvent to binder is 9:1.
According to some embodiments of the application, the electrode paste further comprises a conductive agent that is at least one of conductive carbon black, conductive graphite, carbon nanotubes, graphene, or carbon fiber powder.
According to some embodiments of the application, the conductive agent is graphene and carbon fiber powder. Preferably, the conductive agent is graphene 1 part and carbon fiber powder 1 part by weight. According to some embodiments of the application, the electrode slurry comprises the binder, graphene, carbon fiber powder, and lithium manganese cobalt nickel ternary material.
According to some embodiments of the application, the mass ratio of the binder, graphene, carbon fiber powder and lithium manganese cobalt nickel ternary material is (95-99): (0.5-5): (0.5-5): (1-5): .
According to some embodiments of the application, the electrode slurry has a solids content of 40-75%.
A third aspect of the present application provides a method for producing the above electrode slurry, comprising the steps of: and mixing the active material and a binder to obtain the electrode slurry.
According to some embodiments of the application, the method of manufacturing comprises the steps of: and mixing the adhesive with a solvent, and then sequentially mixing with a conductive agent and an active substance to obtain the electrode slurry.
According to some embodiments of the application, the method of manufacturing comprises the steps of:
(1) Mixing N-methylpyrrolidone with xylene; adding adhesive after stirring uniformly, mixing, stirring at 70 ℃ for 1-3h at a rotating speed of 50-200 r/min;
(2) Adding graphene, and stirring at a rotating speed of 1500-2500r/min for 3-6h;
(3) Adding carbon fiber powder, and stirring at 1500-2500r/min for 30-90min;
(4) Adding metal oxide containing lithium, nickel, cobalt and manganese, and stirring at a rotating speed of 1500-2500r/min for 2-4h to obtain the electrode slurry.
A fourth aspect of the present application provides an electrode sheet including a current collector and an electrode coating layer provided on the current collector; the electrode coating is formed using the electrode paste described above.
According to some embodiments of the application, the current collector is aluminum foil.
A fifth aspect of the present application provides a method for manufacturing the electrode sheet described above, comprising the steps of: and coating the electrode slurry on the surface of the current collector, drying, and performing heat treatment to obtain the electrode plate.
According to some embodiments of the application, the electrode slurry is coated on the surface of an aluminum foil, dried and heat treated to obtain the electrode sheet.
A sixth aspect of the application provides a battery comprising the electrode sheet described above.
According to some embodiments of the application, the battery is a lithium ion battery.
According to some embodiments of the application, the battery comprises a positive electrode plate, a negative electrode plate and a separation membrane, wherein the positive electrode plate is the electrode plate. And the active substance of the positive plate is a lithium nickel cobalt manganese ternary material.
Therefore, the beneficial effects of the application include:
1. the adhesive provided by the application is applied to electrode slurry, and the electrode slurry has good fluidity and stability through the synergistic effect of the poly (chlorotrifluoroethylene) and the polyether-ether-ketone, so that the problems of gel, jelly and agglomeration are avoided;
2. the electrode plate with the adhesive provided by the application has the characteristics of no agglomeration phenomenon on the surface, good toughness, low punching rejection rate and good baking effect;
3. the adhesive, the electrode slurry and the electrode slice provided by the application have simple preparation process and are easy to realize industrialization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below.
The following is a technical scheme of an embodiment of the specific application.
Example 1
The embodiment provides an adhesive which comprises 2 parts by weight of polytrifluoroethylene and 1 part by weight of polyether-ether-ketone.
The embodiment also provides an electrode slurry, which comprises, by weight, 64 parts of polytrifluoroethylene, 32 parts of polyether-ether-ketone, 1 part of graphene, 1 part of carbon fiber powder, 2 parts of lithium-manganese-cobalt-nickel ternary material, 432 parts of xylene and 432 parts of N-methylpyrrolidone.
The preparation method of the electrode slurry comprises the following steps:
(1) Adding the poly (chlorotrifluoroethylene) and the polyether-ether-ketone into a mixed solution of N-methyl pyrrolidone and dimethylbenzene, and stirring at the temperature of 70 ℃ for 2 hours at the rotating speed of 150 r/min;
(2) Adding graphene, and stirring at a rotating speed of 2000r/min for 4 hours;
(3) Adding carbon fiber powder, and stirring at a rotating speed of 2000r/min for 30 minutes;
(4) Adding metal oxide containing lithium, nickel, cobalt and manganese, stirring for 3 hours at a rotating speed of 2000r/min, and obtaining the plasma.
The embodiment also provides an electrode plate, which comprises an aluminum foil current collector and an electrode coating arranged on the aluminum foil current collector, wherein the electrode coating is formed by the electrode slurry provided by the embodiment.
The preparation method of the electrode slice comprises the following steps: and coating the electrode slurry on the surface of an aluminum foil current collector, and then drying for 4-8 hours at 100 ℃ to obtain the electrode plate.
Comparative example 1
The comparative example provides an electrode slurry, which comprises 96 parts by weight of polyvinylidene fluoride, 432 parts by weight of N-methyl pyrrolidone, 432 parts by weight of dimethylbenzene, 1 part by weight of graphene, 1 part by weight of carbon fiber powder and 2 parts by weight of lithium-manganese-cobalt-nickel ternary material.
The preparation method of the electrode slurry comprises the following steps:
(1) Adding polyvinylidene fluoride into a mixed solution of N-methyl pyrrolidone and dimethylbenzene, and stirring at a speed of 150r/min at 70 ℃ for 2 hours;
(2) Adding graphene, and stirring at a rotating speed of 2000r/min for 4 hours;
(3) Adding carbon fiber powder, and stirring at a rotating speed of 2000r/min for 30 minutes;
(4) Adding metal oxide containing lithium, nickel, cobalt and manganese, stirring for 3 hours at a rotating speed of 2000r/min, and obtaining the plasma.
The comparative example also provides an electrode sheet comprising an aluminum foil current collector and an electrode coating provided on the aluminum foil current collector, the electrode coating being formed from the electrode slurry provided in the comparative example.
The preparation method of the electrode slice comprises the following steps: and coating the electrode slurry on the surface of an aluminum foil current collector, and then drying for 4-8 hours at 100 ℃ to obtain the electrode plate.
Comparative example 2
The comparative example provides an electrode slurry, which comprises 96 parts by weight of polytrifluoroethylene, 432 parts by weight of N-methylpyrrolidone, 432 parts by weight of dimethylbenzene, 1 part by weight of graphene, 1 part by weight of carbon fiber powder and 2 parts by weight of lithium-manganese-cobalt-nickel ternary material.
The preparation method of the electrode slurry comprises the following steps:
(1) Adding the poly (chlorotrifluoroethylene) into a mixed solution of N-methyl pyrrolidone and dimethylbenzene, and stirring at the temperature of 70 ℃ for 2 hours at the rotating speed of 150 r/min;
(2) Adding graphene, and stirring at a rotating speed of 2000r/min for 4 hours;
(3) Adding carbon fiber powder, and stirring at a rotating speed of 2000r/min for 30 minutes;
(4) Adding metal oxide containing lithium, nickel, cobalt and manganese, stirring for 3 hours at a rotating speed of 2000r/min, and obtaining the plasma.
The comparative example also provides an electrode sheet comprising an aluminum foil current collector and an electrode coating provided on the aluminum foil current collector, the electrode coating being formed from the electrode slurry provided in the comparative example.
The preparation method of the electrode slice comprises the following steps: and coating the electrode slurry on the surface of an aluminum foil current collector, and then drying for 4-8 hours at 100 ℃ to obtain the electrode plate.
Performance testing
1. The morphology of the electrode pastes provided in example 1 and comparative examples 1-2 was observed;
according to the observation result, the electrode paste provided in comparative example 2 is jelly-like; the electrode slurries provided in example 1 and comparative example 1 were both in the form of stable solutions.
2. The coating effect of the electrode sheet provided in example 1 and comparative examples 1-2 was observed;
according to the observation result, the surface of the electrode plate provided in the comparative example 2 has an agglomeration phenomenon; the electrode sheets provided in example 1 and comparative example 1 were smooth in surface and free from significant agglomeration. The adhesive provided by the application is favorable for improving the coating effect of the electrode plate.
3. The toughness of the electrode sheets provided in example 1 and comparative examples 1-2 was tested.
The toughness test is carried out according to the method for measuring the impact strength of the plastic cantilever beam described in GB/T1843-2008, the adopted sample size is 80mm long by 10mm wide by 4mm thick, and the notch type is A type.
The notched impact strength of the electrode sheets provided in example 1 and comparative example-2 is shown in Table 1.
TABLE 1 notched impact Strength of electrode sheets
| Sample of | Notched impact Strength (kJ/m) 2 ) |
| Electrode sheet provided in example 1 | 9.8 |
| Comparative example 1 provides an electrode sheet | 5.7 |
| Comparative example 2 provides an electrode sheet | 2.3 |
According to Table 1, the notched impact strength of the electrode sheet provided in example 1 was much greater than that provided in comparative examples 1-2.
The electrode plate provided by the application has better toughness.
4. Observe the punching effect of the electrode sheet provided in example 1 and comparative examples 1-2
According to the punching result, the punching rejection rate of the electrode sheet provided in the example 1 is lower than 0.5%, and the punching rejection rate of the electrode sheet structure provided in the comparative example 1 is higher than 7%; comparative example 2 provides an electrode sheet with a die cut rejection rate of greater than 23%.
The electrode sheet provided in the embodiment 1 of the application has better punching effect.
5. The melting temperature, the warp deformation temperature of the electrode coating on the electrode sheet provided in example 1 and comparative examples 1-2 were tested
The melting temperatures and warp deformation temperatures of the electrode coatings on the electrode sheets provided in example 1 and comparative examples 1-2 obtained by the tests are shown in Table 2.
TABLE 2 melting temperature and warp deformation temperature of electrode sheets
| Sample of | Melting temperature (. Degree. C.) | Warp deformation temperature (. Degree. C.) |
| Electrode sheet provided in example 1 | 284 | 249 |
| Comparative example 1 provides an electrode sheet | 210 | 185 |
| Comparative example 2 provides an electrode sheet | 167 | 150 |
According to table 2, the melting temperature and the warp deformation temperature corresponding to the electrode coating on the electrode sheet provided in example 1 are higher than the corresponding parameters of the electrode sheet provided in comparative examples 1-2. The adhesive provided by the application is applied to the electrode plate, is beneficial to improving the melting temperature and the buckling deformation temperature of the electrode coating, and has better baking effect.
Finally, it should be understood that the foregoing embodiments are merely illustrative of the technical solutions of the present application, and that although the present application has been described in detail with reference to the above preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solutions of the present application.
Claims (9)
1. The electrode slurry is characterized by comprising an active substance and a binder, wherein the binder consists of 1.5-6 parts by weight of polytrifluoroethylene and 1 part by weight of polyether-ether-ketone.
2. The electrode slurry of claim 1, wherein the binder has a viscosity of 1000-80000 Pa-S.
3. The electrode slurry of claim 1, wherein the weight ratio of active material to binder is 1: (16-99).
4. The electrode slurry of claim 3, wherein the active material is a lithium-containing metal oxide.
5. The electrode slurry of claim 4, wherein the active material is at least one of a lithium nickel cobalt manganese ternary material, a lithium nickel cobalt aluminum ternary material, or a lithium rich manganese based material.
6. The method for producing an electrode paste according to any one of claims 1 to 5, comprising the steps of:
and mixing the active material and a binder to obtain the electrode slurry.
7. An electrode plate is characterized by comprising a current collector and an electrode coating arranged on the current collector; the electrode coating layer is formed using the electrode slurry according to any one of claims 1 to 5.
8. The method for manufacturing an electrode sheet according to claim 7, comprising the steps of:
and coating the electrode slurry on the surface of the current collector, drying, and performing heat treatment to obtain the electrode plate.
9. A battery comprising the electrode sheet of claim 7.
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